Tissue products treated with a softening composition containing a layered polysiloxane micelle

ABSTRACT

A tissue product having a softening composition applied to at least one side is generally disclosed. The softening composition includes a polysiloxane micelle having a core polysiloxane and an outer layer polysiloxane. The core polysiloxane is more hydrophobic than the outer layer polysiloxane. In one embodiment, the core polysiloxane is an amino-functional polysiloxane, and the outer layer polysiloxane is a polyether polysiloxane. The softening composition can also contain other optional ingredients, such as surfactants and beneficial agents.

BACKGROUND OF THE INVENTION

Consumers use paper-wiping products, such as facial tissues and bathtissues, for a wide variety of applications. Facial tissues are not onlyused for nose care but, in addition to other uses, may also be used as ageneral wiping product. Consequently, there are many different types oftissue products currently commercially available.

In some applications, tissue products are treated with softening agentsin order to increase the softness of the tissue. Adding softening agentsto a tissue may impart improved softness to the tissue while maintainingthe tissue's strength and reducing the amount of lint produced by thetissue during use. For example, tissue products treated withamino-functional polysiloxanes have a silky-soft handfeel. In additionto polysiloxanes, long chain alkyl chemicals are also used as softeners.These chemicals provide tissue products with a lotiony, greasy-softhandfeel.

In some applications, tissue products may be treated with otherbeneficial agents as well. For example, in addition to softening agentssuch as polysiloxane lotions, other desirable agents may be added to atissue in order to provide a benefit to the user. For example, vitamins,plant extracts, medications, antimicrobial compounds, and the like mayalso be added to the web in order to transfer the desired agent to theconsumer upon use.

Some additives, however, such as softening agents, may have a tendencyto impart hydrophobicity to the treated tissue web, reducing thewettability characteristics of the web. Although hydrophobicity may bedesirable in some applications, in other applications, increasedhydrophobicity may adversely affect the product. For instance, increasedhydrophobicity in a bath tissue may prevent the bath tissue from beingwetted in a sufficient amount of time and prevent disintegration anddispersing when disposed in a commode or toilet. Hence, in someapplications, it is difficult to find a proper balance between softnessand absorbency, both of which are desirable attributes for tissues,particularly bath tissues.

Thus, a need currently exists for a softening composition that, whenuniformly treated on the surface of a tissue product can provide theproduct with a lotiony-soft handfeel without completely degrading thewettability characteristics of the product.

SUMMARY OF THE INVENTION

In general, one embodiment of the present invention is directed to atissue product comprising at least one tissue web containing pulpfibers. The tissue product has a first side and a second side. Asoftening composition is applied to at least one side of the tissueproduct. The softening composition includes a polysiloxane micellehaving a core polysiloxane and an outer layer polysiloxane. The corepolysiloxane is more hydrophobic than the outer layer polysiloxane. Thesoftening composition can further include at least one beneficial agent.

In one embodiment, the softening composition can be applied to bothsides of the tissue product. For instance, the softening composition canbe applied to each side of the tissue product so as to cover from about40% to about 95% of the surface area of each side of the product. Thepolysiloxane micelle can be applied to the tissue product at a totaladd-on level of from about 0.25% to about 8% by weight, such as fromabout 0.5% to about 5% by weight.

In one embodiment, the core polysiloxane can comprise anamino-functional polysiloxane, such as a polysiloxane having thefollowing structure:

-   -   wherein,    -   m is 10 to 100,000;    -   n is 1 to 5,000;    -   G₁ is R₈ or R₁₀—[X—R₁₁]_(s)—Y—R₁₂;    -   G₂ are independently R₉, a hydroxyl radical, an alkoxyl radical,        or R₁₀—[X—R₁₁]_(s)—Y—R₁₂;    -   R₁ through R₉ are independently selected from the group        consisting of C₁ to C₈ substituted or unsubstituted, aliphatic        or aromatic alkyl radicals;    -   R₁₀ and R₁₁ are independently a substituted or unsubstituted C₂        to C₆ alkylene diradical;    -   X and Y are independently a NR₁₃ diradical;    -   R₁₂ and R₁₃ are independently a hydrogen or a substituted or        unsubstituted C₁ to C₂₀ alkyl radical; and    -   S is 0 or 1.

In one particular embodiment, the outer layer polysiloxane can comprisea polyether polysiloxane, such as a polysiloxane having the followingstructure:

wherein, x and z are integers >0, y is an integer ≧0; the mole ratio ofx to (x+y+z) is from about 0.05 percent to about 95 percent; the ratioof y to (x+y+z) is from about 0 percent to about 25%; the R⁰-R⁹ moietiesare independently selected from the organofunctional group consisting ofC₁ or higher alkyl groups, ethers, polyethers, polyesters, amines,imines, amides, and alkyl and alkenyl analogues of such groups; the R¹⁰moiety is an amino functional moiety; R¹¹ is a polyether functionalgroup having the generic formula: R¹²—(R¹³—O)_(a)—(R¹⁴O)_(b)—R¹⁵,wherein R¹², R¹³, and R¹⁴ are independently C₁₋₄alkyl groups, linear orbranched; R¹⁵ is H or a C₁₋₃₀ alkyl group; and, “a” and “b” are integersof from about 1 to about 100.

In another embodiment, the present invention is directed to a method ofmaking a tissue product. The method includes forming a tissue webcontaining pulp fibers and applying a softening composition to at leastone side of the tissue product. The softening composition comprising apolysiloxane micelle having a core polysiloxane and an outer layerpolysiloxane. The core polysiloxane is more hydrophobic than said outerlayer polysiloxane.

Other features and aspects of the present invention are discussed ingreater detail below.

BRIEF DESCRIPTION OF THE DRAWINGS

A full and enabling disclosure of the present invention, including thebest mode thereof to one skilled in the art, is set forth moreparticularly in the remainder of the specification, including referenceto the accompanying figures, in which:

FIG. 1 is a representation of an exemplary polysiloxane micelle;

FIG. 2 is a representation of an exemplary surfactant stabilizedpolysiloxane micelle;

FIG. 3 is a schematic diagram of an uncreped through-air dried processfor making tissue webs; and

FIG. 4 is a schematic diagram of one embodiment for applying a softeningcomposition to both sides of a tissue web.

Repeat use of reference characters in the present specification anddrawings is intended to represent the same or analogous features of theinvention.

DETAILED DESCRIPTION OF THE INVENTION

Reference now will be made to the embodiments of the invention, one ormore examples of which are set forth below. Each example is provided byway of explanation of the invention, not as a limitation of theinvention. In fact, it will be apparent to those skilled in the art thatvarious modifications and variations may be made in the inventionwithout departing from the scope or spirit of the invention. Forinstance, features illustrated or described as part of one embodimentmay be used in another, embodiment to yield a still further embodiment.Thus, it is intended that the present invention cover such modificationsand variations as come within the scope of the appended claims and theirequivalents. It is to be understood by one of ordinary skill in the artthat the present discussion is a description of exemplary embodimentsonly, and is not intended as limiting the broader aspects of the presentinvention, which broader aspects are embodied in the exemplaryconstructions.

In general, one embodiment of the present invention is directed to asoftening composition for a tissue product in order to provide theproduct with a non-greasy, lotiony-soft handfeel. Also, the softeningcomposition of the present invention has been formulated such that thecomposition may be applied to a tissue product without substantiallyinterfering with the wettability characteristics of the product.

More particularly, the softening composition is applied to the tissue inan emulsion containing a layered polysiloxane micelle. The layeredpolysiloxane micelle includes a core of a first polysiloxane surroundedby at least one outer layer of a second, different polysiloxane. Forexample, the polysiloxane of the core of the micelle can be morehydrophobic than the polysiloxane of the outer layer(s). Referring toFIG. 1, an exemplary polysiloxane micelle 100 having a core 105 and anouter layer 110. Although only one outer layer 110 is shown, additionalpolysiloxane outer layers can be included in the micelle. It is alsonoted that the polysiloxane micelle 100 is actually a 3-dimensionalmicelle, though it is depicted in only 2-dimensions.

Of particular advantage, utilizing a polysiloxane micelle having twodifferent polysiloxanes forming the core and the outer layer allowscertain properties and characteristics of both polysiloxanes to bemaximized, while minimizing or avoiding other disadvantageous propertiesof the polysiloxanes.

Polysiloxanes encompass a very broad class of compounds. They arecharacterized in having a backbone structure:

where R′ and R″ can be a broad range of organo and non-organo groupsincluding mixtures of such groups and where n is an integer greater than2. These polysiloxanes may be linear, branched or cyclic. They include awide variety of polysiloxane copolymers containing various compositionsof functional groups, hence, R′ and R″ actually may represent manydifferent types of groups within the same polymer molecule. The organoor non-organo groups may be capable of reacting with cellulose tocovalently, ionically or hydrogen bond the polysiloxane to thecellulose. These functional groups may also be capable of reacting withthemselves to form crosslinked matrixes with the cellulose. Forinstance, when R′ and R″ are alkyl groups, such as C₁-C₃₀ linear orbranched alkyl groups, the polysiloxane component is referred to as apolydialkylsiloxane component.

Functionalized polysiloxanes and their aqueous emulsions are well knowncommercially available materials. The functional groups on thepolysiloxanes can affect the hydrophobicity characteristics of thepolysiloxane. In order to produce the polysiloxane micelle of thesoftening composition, the polysiloxanes of the core have morehydrophobic functional groups than the functional groups of the outerlayer(s) polysiloxane(s). Thus, the more hydrophilic outer layerpolysiloxane can help stabilize a more hydrophobic polysiloxane in anaqueous emulsion. For instance, a relatively hydrophobic polysiloxanethat is likely to phase separate under normal conditions in water can bestabilized by surrounding it with an outer layer of a more hydrophilicpolysiloxane. In this case, the more hydrophilic polysiloxane acts muchlike a surfactant agent.

One class of functionalized polysiloxanes is amino-functionalpolysiloxanes, which generally have the following structure:

wherein, x and y are integers >0. The mole ratio of x to (x+y) can befrom about 0.005 percent to about 25 percent. The R¹-R⁹ moieties can beindependently any organofunctional group including C₁ or higher alkylgroups, ethers, polyethers, polyesters, amines, imines, amides, or otherfunctional groups including the alkyl and alkenyl analogues of suchgroups. The R¹⁰ moiety is an amino functional moiety including but notlimited to primary amine, secondary amine, tertiary amines, quaternaryamines, unsubstituted amides and mixtures thereof. An exemplary R¹⁰moiety contains one amine group per constituent or two or more aminegroups per substituent, separated by a linear or branched alkyl chain ofC₁ or greater. When R⁷ and R⁸ are alkyl groups such as C₁-C₈ alkylgroups the polysiloxanes are hereinafter referred to as aminofunctionalpolysiloxanes, more specifically amino functional polydialkylsiloxanes.Exemplary materials include DC 2-8220 and DC2-8182 commerciallyavailable from Dow Corning, Inc., Midland, Mich. and Y-14344 availablefrom Crompton, Corp., Greenwich, Conn.

In one embodiment, the amino-functional polysiloxane may have thefollowing structure:

-   -   wherein,    -   m is 10 to 100,000;    -   n is 1 to 5,000;    -   G₁ is R₈ or R₁₀—[X—R₁₁]_(s)—Y—R₁₂;    -   G₂ are independently R₉, a hydroxyl radical, an alkoxyl radical,        or R₁₀—[X—R₁₁]_(s)—Y—R₁₂;    -   R₁ through R₉ are independently selected from the group        consisting of C₁ to C₈ substituted or unsubstituted, aliphatic        or aromatic alkyl radicals;    -   R₁₀ and R₁₁ are independently a substituted or an unsubstituted        C₂ to C₆ alkylene diradical;    -   X and Y are independently a NR₁₃ diradical;    -   R₁₂ and R₁₃ are independently a hydrogen or a substituted or        unsubstituted C₁ to C₂₀ alkyl radical; and    -   S is 0 or 1.

Representative species within the foregoing general structure includethe following:

Commercially available amino-functional polysiloxanes that may be madeaccording to the above structures are marketed by Kelmar Industries,Inc. under the tradenames AF-21, AF-23, AF-26 and HAF-1130.

According to one embodiment of the present invention, theamino-functional polysiloxanes can be utilized to form the polysiloxanecore of the micelle. This amino-functional polysiloxane core can besurrounded by an outer layer of another class of functionalizedpolysiloxanes having a more hyrophilic functional group(s), such aspolyether polysiloxanes, which are generally more hydrophilic than theamino-functional polysiloxanes.

Such polyether polysiloxanes generally have the following structure:

wherein, x and z are integers >0, y is an integer ≧0. The mole ratio ofx to (x+y+z) can be from about 0.05 percent to about 95 percent. Theratio of y to (x+y+z) can be from about 0 percent to about 25%. TheR⁰-R⁹ moieties can be independently any organofunctional group includingC₁ or higher alkyl groups, ethers, polyethers, polyesters, amines,imines, amides, or other functional groups including the alkyl andalkenyl analogues of such groups. The R¹⁰ moiety is an amino functionalmoiety including but not limited to primary amine, secondary amine,tertiary amines, quaternary amines, unsubstituted amides and mixturesthereof. An exemplary R¹⁰ moiety contains one amine group perconstituent or two or more amine groups per substituent, separated by alinear or branched alkyl chain of C¹ or greater. R¹¹ is a polyetherfunctional group having the generic formula:R¹²—(R¹³—O)_(a)—(R¹⁴O)_(b)—R¹⁵, wherein R¹², R¹³, and R¹⁴ areindependently C₁₋₄ alkyl groups, linear or branched; R¹⁵ can be H or aC₁₋₃₀ alkyl group; and, “a” and “b” are integers of from about 1 toabout 100, more specifically from about 5 to about 30.

When R⁷-R⁸ are alkyl groups such as C₁-C₈ alkyl groups, and y and z areboth >0 the polysiloxanes are usually referred to as amino functionalpolyetherpolydialkylsiloxane copolymers. Such definition also applies tocases where y=0 but R¹¹ contains amine functional polyether groups.

Exemplary aminofunctional polyetherpolysiloxanes and aminofunctionalpolyetherpolydialkylsiloxanes are the Wetsoft® CTW family manufacturedand sold by Wacker, Inc., Adrian, Mich. For example, thepolyetherpolysiloxanes in the Wetsoft® CTW is believed to have thefollowing structure:

Other exemplary polysiloxanes can be found in U.S. Pat. No. 6,432,270 byLiu, et.al, and incorporated by reference herein.

In one embodiment, the polysiloxane micelle can be formed from arelatively small amount of the outer layer polysiloxane, when comparedto the amount of the core polysiloxane. For example, the corepolysiloxane can be greater than 50% by weight of the total amount ofpolysiloxane in the polysiloxane micelle, such as greater than about60%. In some embodiments, the core polysiloxane can be greater than 70%by weight of the total amount of polysiloxane in the polysiloxanemicelle, such as greater than about 80%. Conversely, the outer layerpolysiloxane can be from about 5% to about 50% by weight of thepolysiloxane micelle, such as from about 10% to about 40% by weight. Forinstance, in one embodiment, the outer layer polysiloxane can be fromabout 10% to about 30% by weight of the polysiloxane micelle, such asfrom about 15% to about 25% by weight.

Even though amount of outer layer polysiloxane in the polysiloxanemicelle is relatively small, the properties of the outer layer canovershadow those of the core polysiloxane, especially while still in anemulsion form. Thus, a less expensive polysiloxane can be used for thecore, while still benefiting from the properties of the outer layerpolysiloxane.

The polysiloxane micelle can be present in the softening composition inan amount from about 2% to about 50% by weight, such as from about 5% toabout 30% by weight, and such as from about 20% to about 30% by weight.In other embodiments, the polysiloxane micelle can be present in agreater weight present of the softening composition, such as greaterthan about 30% by weight and greater than about 40% by weight.

In one particular embodiment, the polysiloxane micelle can be utilizedin combination with a surfactant. For example, referring to FIG. 2, apolysiloxane micelle 100 is shown have a core 105 and an outer layer110. Surfactants 115 are shown interacting with the polysiloxane of theouter layer 110. The surfactant 115 is used to form a layer between theouter layer 110 and the water of the emulsion, stabilizing thepolysiloxane of the outer layer 110 in the aqueous emulsion.

Examples of non-ionic surfactants include, but are not limited topolyoxyethylene alkylamines, trialkylamine oxides, triethanol aminefatty acid esters and partial fatty acid esters, polyoxyethylene alkylethers such as those obtained by ethoxylation of long chain alcohols,polyoxyethylene alkenyl ethers, alkylphenyl ethoxylates, polyoxyethylenepolystyrlphenyl ethers, polypropylene glycol fatty acid esters and alkylethers, polyethylene glycol fatty acid esters and alkyl ethers,polyhydric alcohol fatty acid partial esters and alkyl ethers, glycerinfatty acid esters, polyglycerin fatty acid esters, polyoxyethylenepolyhydric alcohol fatty acid partial esters and alkyl ethers,polyoxyethylene sorbitan fatty acid esters, polyoxyethylene glycerinfatty acid esters, polyoxyethylene fatty acid esters and alkyl ethers,polyglycerin fatty acid esters, ethoxylated/propoxylated vegetable oilsand the like including mixtures of said surfactants.

Examples of ionic surfactants include primary, secondary and tertiaryamine salts of the corresponding alkyl amines, alkyltrimethyl ammoniumsalts, dialkyldimethyl benzonium salts, dialkyldimethyl ammonium salts,trialkylmethyl ammonium salts, tetra alkyl ammonium salts,polyethylenepolyamine fatty acid amide salts, fatty acid salts,alkylbenzenesulfonates, dialkylsulfosuccinates, alkylsulfonates,N-acyl-N-methyltaurate, alkylsulfates, sulfonated fats and oils,polyoxyethylene alkylether sulfonates, polyoxyethylene styrenated phenylether sulfonates, alkyphosphates, polyoxyethylene alkyl phenyl etherphosphates, N,N-dimethyl-N-alkyl-N-carboxymethylammonium betaines,N,N-dialkylaminoalkylene carboxylates,N,N,N-trialkyl-N-sulfoalkeneammonium betaines,N,N-dialkyl-N,N-bispolyoxyethyleneammonium sulfate ester betaines, andthe like including mixtures of such surfactants.

In addition to the polysiloxane micelle and, optionally, a surfactant,the softening composition may contain of other beneficial agents, suchas a skin conditioning agent. For instance, in one embodiment, thecomposition may contain aloe, Vitamin E, a herb, or a herb extract.Other beneficial agents that may be included in the composition include,without limitation, anti-acne actives, antimicrobial actives, antifungalactives, antiseptic actives, antioxidants, cosmetic astringents, drugastringents, biological additives, deodorants, emollients, externalanalgesics, film formers, fragrances, humectants, natural moisturizingagents and other skin moisturizing ingredients known in the art such aslanolin, opacifiers, skin exfoliating agents, skin protectants,solvents, sunscreens, and surfactants.

In general, any suitable tissue product may be treated in accordancewith the present invention. The tissue product may be a single plyproduct or a multi-ply product. The plies of the tissue product maygenerally be formed in any of a variety of papermaking processes knownin the art. In fact, any process capable of forming a tissue web may beutilized in the present invention. For example, tissue making processesof the present invention may utilize adhesive creping, wet creping,double creping, embossing, wet-pressing, air pressing, through-airdrying, creped through-air drying, uncreped through-air drying, as wellas other steps known in the art.

Tissue products that may be treated in accordance with the presentinvention include not only bath tissue and facial tissue, but may alsoinclude paper towels and industrial wipers. The tissue products may havea basis weight up to about 120 gsm, such as from about 6 gsm to about 80gsm. Bath tissues and facial tissues, for instance, may have a basisweight of from about 10 gsm to about 45 gsm, such as from about 30 gsmto about 40 gsm.

In one particular embodiment, the softening composition of the presentinvention is applied to a single ply uncreped through-air dried web.Referring to FIG. 3, shown is a schematic flow diagram of athroughdrying process for making uncreped throughdried tissue sheets.Shown is the headbox 1 which deposits an aqueous suspension ofpapermaking fibers onto an inner forming fabric 3 as it traverses theforming roll 4. Outer forming fabric 5 serves to contain the web whileit passes over the forming roll and sheds some of the water. The wet web6 is then transferred from the inner forming fabric to a wet endtransfer fabric 8 with the aid of a vacuum transfer shoe 9. Thistransfer is preferably carried out with the transfer fabric traveling ata slower speed than the forming fabric (rush transfer) to impart stretchinto the final tissue sheet.

The wet web is then transferred to the throughdrying fabric 11 with theassistance of a vacuum transfer roll 12. The throughdrying fabriccarries the web over the throughdryer 13, which blows hot air throughthe web to dry it while preserving bulk. There can be more than onethroughdryer in series (not shown), depending on the speed and the dryercapacity.

The dried tissue sheet 15 is then transferred to a first dry endtransfer fabric 16 with the aid of vacuum transfer roll 17. The tissuesheet shortly after transfer is sandwiched between the first dry endtransfer fabric and the transfer belt 18 to positively control the sheetpath. The air permeability of the transfer belt is lower than that ofthe first dry end transfer fabric, causing the sheet to naturally adhereto the transfer belt. At the point of separation, the sheet follows thetransfer belt due to vacuum action. Suitable low air permeabilityfabrics for use as transfer belts include, without limitation, COFPAMononap NP 50 dryer felt (air permeability of about 50 cubic feet perminute per square foot) and Asten 960C (impermeable to air). Thetransfer belt passes over two winding drums 21 and 22 before returningto pick up the dried tissue sheet again. The sheet is transferred to theparent roll 25 at a point between the two winding drums. The parent rollis wound onto a reel spool 26, which is driven by a center drive motor.

Particularly suitable methods of producing uncreped throughdriedbasesheets for purposes of this invention are described in U.S. Pat. No.6,017,417 issued Jan. 25, 2000 to Wendt et al. and U.S. Pat. No.5,944,273 issued Aug. 31, 1999 to Lin et al., both of which are hereinincorporated by reference.

The softening composition as described above may be applied to a singleside of a tissue product or may be applied to opposite sides. In orderto maximize an increase in softness, the softening composition may beapplied to both sides of the tissue product. When added to the tissueproduct, the total solids add-on is generally less than about 5% byweight, such as less than about 4% by weight, or less than about 3% byweight. For example, in one embodiment, the total solids add-on may befrom about 0.5% by weight to about 2.5% by weight. When applied to thetissue product, the softening composition may cover from about 20% toabout 100% of the surface area of both sides of the product, such asfrom about 40% to about 95% of the surface area of each side.

As mentioned above, the softening composition of the present inventionhas been found to not only improve the handfeel of tissue products, butmay also be applied so as to minimize any increase in wettability. Forinstance, softening compositions containing the above proportion ofingredients at the above add-on amounts may be applied to a bath tissuethat still retains a wet-out time of less than about 8 seconds, such asless than about 7 seconds. For example, in one embodiment, the wet-outtime of a tissue product treated in accordance with the presentinvention may be less than about 6 seconds, and even less than about 5seconds. For purposes of comparison, an untreated tissue product mayhave a wet-out time of from about 3 seconds to about 4 seconds.

The softening composition may be applied to the tissue product using anysuitable method or technique without limitation. For instance, thesoftening composition may be sprayed onto the tissue product or printedonto the tissue product. When sprayed or printed onto a tissue sheet,the softening composition may be combined with water, preservatives,anti-foamers, and surfactants to form an emulsion. Water, for instance,may be combined with a softening composition in order to reduce theviscosity in order to print or spray the composition onto a tissue web.

In one particular embodiment, the softening composition is contained inan emulsion and applied to a tissue web using an offset rotogravureprinter as particularly illustrated in FIG. 4. When the softeningcomposition is contained in an emulsion and applied to a tissue productby printing or spraying, the softening composition may comprise fromabout 10% to 60% by weight of the emulsion, such as from about 20% toabout 50% by weight of the emulsion. In one particular embodiment, forinstance, the softening composition may comprise from about 25% to about45% by weight of the emulsion.

Referring to FIG. 4, shown is the parent roll 25 being unwound andpassed through two calender nips between calender rolls 30 a and 31 aand 30 b and 31 b. The calendered web is then passed to the rotogravurecoating station comprising a first closed doctor chamber 33 containingthe emulsion of the softening composition to be applied to a first sideof the web, a first engraved steel gravure roll 34, a first rubberbacking roll 35, a second rubber backing roll 36, a second engravedsteel gravure roll 37 and a second closed doctor chamber 38 containingthe emulsion of the softening composition to be applied to the secondside of the web. If both sides of the web are to be treated, the twoemulsions can be the same or different. The calendered web passesthrough a fixed-gap nip between the two rubber backing rolls where theemulsion of the softening composition is applied to the web. The treatedweb is then passed to the rewinder where the web is wound onto logs 40and slit into rolls of bath tissue.

EXAMPLES

An amino-functional polysiloxane (AF-23, Kelmar Industries, Inc.) wascombined with a polyether polysiloxane (Wetsoft® CTW, Wacker, Inc.,Adrian, Mich.) to form an aqueous emulsion. Other ingredients in theemulsion include Pulpsil KCD50EN is a defoamer available from WackerChemical, Kelmar Division (Duncan, S.C.); SM-205P is a biocidepreservative available from Wacker Chemical, Kelmar Division (Duncan,S.C.); and TDA-9C is a ethylated alcohol surfactant available fromWacker Chemical, Kelmar Division (Duncan, S.C.).

TABLE 1 Ingredient Weight Percent AF-23 6.5 CTW 1 Pulpsil KCD50EN 0.5SM-205P 0.77 TDA-9C 22.5 water 68.73

For comparison, two softening compositions were also made, each havingonly one polysiloxane present:

TABLE 2 (Control A) Ingredient Weight Percent CTW 25 Pulpsil KCD50EN 0.5SM-205P 0.77 TDA-9C 6 water 67.73

TABLE 3 (Control B) Ingredient Weight Percent AF-23 7.5 Pulpsil KCD50EN0.5 SM-205P 0.77 TDA-9C 22.5 water 68.73

It was found that the two polysiloxanes used in the formulation of Table1 formed a micelle with the polyether polysiloxane (Wetsoft® CTW,Wacker, Inc., Adrian, Mich.) as an outer layer of the amino-functionalpolysiloxane (AF-23, Kelmar Industries, Inc.) core. Also, the presentinventors have found that surrounding the amino-functional polysiloxane(AF-23, Kelmar Industries, Inc.) with an outer layer of the morehydrophilic polyether polysiloxane (Wetsoft® CTW, Wacker, Inc., Adrian,Mich.), the processing characteristics of the amino-functionalpolysiloxane (AF-23, Kelmar Industries, Inc.) have been substantiallyimproved. For instance, when used alone, the amino-functionalpolysiloxane (AF-23, Kelmar Industries, Inc.) has been known to readilyphase separate in the emulsion. However, when used in combination withthe polyether polysiloxane (Wetsoft® CTW, Wacker, Inc., Adrian, Mich.),the emulsion was much more stable to heat and shear forces.

Each of the emulsions described above, was applied to the bath tissueaccording to the process described in FIG. 4, with an add-on level ofabout 0.466 lb/1000 ft². Panel tests revealed that tissue applied withthe Control B emulsion, was less soft than tissue applied with theControl A emulsion; both tissue samples had similar stiffness results.

The tissue including the polysiloxane micelle emulsion of Table 1 showedimprovement over the Control A tissue. Panel tests showed that thepolysiloxane micelle emulsion gave the tissue more softness,significantly less stiffness, significantly less greasy tissue feel andresidue, significantly less coating felt on the tissue, significantlymore waxy tissue feel and residue, and significantly less odor intensityand objectionable odor, as compared to Control A. Bench testing resultsmeasuring Overall Softness, showed that the tissue with polysiloxanemicelle emulsion applied is softer than the tissue with Control Aapplied.

Panel tests which compared the polysiloxane micelle emulsion, of Table1, to Control B, revealed that the polysiloxane micelle emulsion gavethe tissue significantly more softness and significantly less stiffness,as well as less odor intensity and objectionable odor over the Control Btissue. Bench testing results measuring Overall Softness, showed thatthe tissue with polysiloxane micelle emulsion applied is softer than thetissue with Control B applied.

The tissue including the polysiloxane micelle emulsion of Table 1 alsoshowed improvement over the Control A tissue in the following areas:less greasy tissue feel, less greasy residue, less coating felt on thetissue, more waxy tissue residue, and significantly less odor intensityand objectionable odor. The tissue including the polysiloxane micelleemulsion of Table 1 also showed less odor intensity and objectionableodor over the Control B tissue.

These and other modifications and variations to the present inventionmay be practiced by those of ordinary skill in the art, withoutdeparting from the spirit and scope of the present invention, which ismore particularly set forth in the appended claims. In addition, itshould be understood that aspects of the various embodiments may beinterchanged both in whole or in part. Furthermore, those of ordinaryskill in the art will appreciate that the foregoing description is byway of example only, and is not intended to limit the invention sofurther described in such appended claims.

1. A tissue product comprising: at least one tissue web containing pulpfibers, the tissue product having a first side and a second-side; asoftening composition applied to at least one side of the tissueproduct, the softening composition comprising a polysiloxane micelle,said polysiloxane micelle comprising a core polysiloxane and an outerlayer polysiloxane, wherein said core polysiloxane is more hydrophobicthan said outer layer polysiloxane.
 2. A tissue product as in claim 1,wherein said core polysiloxane comprises an amino-functionalpolysiloxane having the following structure:

wherein, m is 10 to 100,000; n is 1 to 5,000; G₁ is R₈ orR₁₀—[X—R₁₁]_(s)—Y—R₁₂; G₂ are independently R₉, a hydroxyl radical, analkoxyl radical, or R₁₀—[X—R₁₁]_(s)—Y—R₁₂; R₁ through R₉ areindependently selected from the group consisting of C₁ to C₈ substitutedor unsubstituted, aliphatic or aromatic alkyl radicals; R₁₀ and R₁₁ areindependently a substituted or unsubstituted C₂ to C₆ alkylenediradical; X and Y are independently a NR₁₃ diradical; R₁₂ and R₁₃ areindependently a hydrogen or a substituted or unsubstituted C₁ to C₂₀alkyl radical; and S is 0 or
 1. 3. A tissue product as defined in claim1, wherein the softening composition has been applied to both sides ofthe tissue product, and wherein the polysiloxane micelle is applied tothe tissue product at a total add-on level of from about 0.25% to about8% by weight.
 4. A tissue product as defined in claim 3, wherein thepolysiloxane micelle is applied to the tissue product at a total add-onlevel of from about 0.5% to about 5% by weight.
 5. A tissue product asdefined in claim 3, wherein the softening composition is applied to eachside of the tissue product so as to cover from about 40% to about 95% ofthe surface area of each side of the product.
 6. A tissue product asdefined in claim 1, wherein said core polysiloxane comprises anamino-functional polysiloxane selected from the group consisting of


7. A tissue product as in claim 1, wherein said outer layer polysiloxanecomprises a polyether polysiloxane.
 8. A tissue product as in claim 7,wherein said core polysiloxane comprises an amino-functionalpolysiloxane.
 9. A tissue product as in claim 7, wherein said outerlayer polysiloxane has the following structure:

wherein, x and z are integers >0, y is an integer ≧0; the mole ratio ofx to (x+y+z) is from about 0.05 percent to about 95 percent; the ratioof y to (x+y+z) is from about 0 percent to about 25%; the R⁰-R⁹ moietiesare independently selected from the organofunctional group consisting ofC₁ or higher alkyl groups, ethers, polyethers, polyesters, amines,imines, amides, and alkyl and alkenyl analogues of such groups; the R¹⁰moiety is an amino functional moiety; R¹¹ is a polyether functionalgroup having the generic formula: R¹²—(R¹³—O)_(a)—(R¹⁴O)_(b)—R¹⁵,wherein R¹², R¹³, and R¹⁴ are independently C₁₋₄alkyl groups, linear orbranched; R¹⁵ is H or a C₁₋₃₀ alkyl group; and, “a” and “b” are integersof from about 1 to about
 100. 10. A tissue product as in claim 7,wherein said outer layer polysiloxane has the following structure:

wherein x is an integer from 40 to 150; y is an integer from 1 to 5; zis an integer from 1 to 5; n is an integer from 10 to 30; and m is aninteger from 10 to
 30. 11. A tissue product as in claim 1, wherein saidsoftening composition further comprises at least one beneficial agent.12. A tissue product comprising: at least one tissue web containing pulpfibers, the tissue product having a first side and a second side; asoftening composition applied to at least one side of the tissueproduct, the softening composition comprising a polysiloxane micelle anda surfactant, said polysiloxane micelle comprising a core polysiloxaneand an outer layer polysiloxane, wherein said core polysiloxanecomprises an amino-functional polysiloxane having the followingstructure:

wherein, m is 10 to 100,000; n is 1 to 5,000; G₁ is R₈ orR₁₀—[X—R₁₁]_(s)—Y—R₁₂; G₂ are independently R₉, a hydroxyl radical, analkoxyl radical, or R₁₀—[X—R₁₁]₉—Y—R₁₂; R₁ through R₉ are independentlyselected from the group consisting of C₁ to C₈ substituted orunsubstituted, aliphatic or aromatic alkyl radicals; R₁₀ and R₁₁ areindependently a substituted or unsubstituted C₂ to C₆ alkylenediradical; X and Y are independently a NR₁₃ diradical; R₁₂ and R₁₃ areindependently a hydrogen or a substituted or unsubstituted C₁ to C₂₀alkyl radical; and S is 0 or 1; and wherein said outer layerpolysiloxane has the following structure:

wherein, x and z are integers >0, y is an integer ≧0; the mole ratio ofx to (x+y+z) is from about 0.05 percent to about 95 percent; the ratioof y to (x+y+z) is from about 0 percent to about 25%; the R⁰-R⁹ moietiesare independently selected from the organofunctional group consisting ofC₁ or higher alkyl groups, ethers, polyethers, polyesters, amines,imines, amides, and alkyl and alkenyl analogues of such groups; the R¹⁰moiety is an amino functional moiety; R¹¹ is a polyether functionalgroup having the generic formula: R¹²—(R¹³—O)_(a)—(R¹⁴)_(b)—R¹⁵ whereinR¹², R¹³, and R¹⁴ are independently C₁₋₄ alkyl groups, linear orbranched; R¹⁵ is H or a C₁₋₃₀ alkyl group; and, “a” and “b” are integersof from about 1 to about
 100. 13. A tissue product as in claim 12,wherein said outer layer polysiloxane has the following structure:

wherein x is an integer from 40 to 150; y is an integer from 1 to 5; zis an integer from 1 to 5; n is an integer from 10 to 30; and m is aninteger from 10 to
 30. 14. A tissue product as in claim 12, wherein saidcore polysiloxane comprises an amino-functional polysiloxane selectedfrom the group consisting of


15. A method of making a tissue product comprising forming a tissue webcontaining pulp fibers, the tissue product having a first side and asecond side; applying a softening composition to at least one side ofthe tissue product, the softening composition comprising a polysiloxanemicelle, said polysiloxane micelle comprising a core polysiloxane and anouter layer polysiloxane, wherein said core polysiloxane is morehydrophobic than said outer layer polysiloxane.
 16. A method as in claim15, wherein said core polysiloxane comprises an amino-functionalpolysiloxane having the following structure:

wherein, m is 10 to 100,000; n is 1 to 5,000; G₁ is R₈ orR₁₀—[X—R₁₁]_(s)—Y—R₁₂; G₂ are independently R₉, a hydroxyl radical, analkoxyl radical, or R₁₀—[X—R₁]_(s)—Y—R₁₂; R₁ through R₉ areindependently selected from the group consisting of C₁ to C₈ substitutedor unsubstituted, aliphatic or aromatic alkyl radicals; R₁₀ and R₁₁ areindependently a substituted or unsubstituted C₂ to C₆ alkylenediradical; X and Y are independently a NR₁₃ diradical; R₁₂ and R₁₃ areindependently a hydrogen or a substituted or unsubstituted C₁ to C₂₀alkyl radical; and S is 0 or
 1. 17. A method as in claim 15, wherein thesoftening composition has been applied to both sides of the tissueproduct, the softening composition being applied to the tissue productsuch that the total solids add-on is from about 0.5% to about 5% byweight.
 18. A method as in claim 15, wherein the softening compositionis applied to each side of the tissue product so as to cover from about40% to about 95% of the surface area of each side of the product.
 19. Amethod as in claim 15, wherein said core polysiloxane comprises anamino-functional polysiloxane selected from the group consisting of


20. A method as in claim 15, wherein said outer layer polysiloxanecomprises a polyether polysiloxane.
 21. A method as in claim 20, whereinsaid core polysiloxane comprises a amino-functional polysiloxane.
 22. Amethod as in claim 15, wherein said outer layer polysiloxane has thefollowing structure:

wherein, x and z are integers >0, y is an integer ≧0; the mole ratio ofx to (x+y+z) is from about 0.05 percent to about 95 percent; the ratioof y to (x+y+z) is from about 0 percent to about 25%; the R⁰-R⁹ moietiesare independently selected from the organofunctional group consisting ofC₁ or higher alkyl groups, ethers, polyethers, polyesters, amines,imines, amides, and alkyl and alkenyl analogues of such groups; the R¹⁰moiety is an amino functional moiety; R¹¹ is a polyether functionalgroup having the generic formula: R¹²—(R¹³—O)_(a)—(R¹⁴O)_(b)—R¹⁵,wherein R¹², R¹³, and R¹⁴ are independently C₁₋₄ alkyl groups, linear orbranched; R¹⁵ is H or a C₁₋₃₀ alkyl group; and, “a” and “b” are integersof from about 1 to about
 100. 23. A method as in claim 15, wherein saidouter layer polysiloxane has the following structure:

wherein x is an integer from 40 to 150; y is an integer from 1 to 5; zis an integer from 1 to 5; n is an integer from 10 to 30; and m is aninteger from 10 to
 30. 24. A method as in claim 15, wherein thesoftening composition further comprises at least one beneficial agent.25. A method as in claim 15, wherein the softening composition furthercomprises a surfactant.